The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to β-agostic complexes in which palladium can rapidly migrate along the chain (“chain-walking”) through β-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile.
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